CN1277321C - Method of prepn, of positive electrode laminated cell lithium manganate of lithium ion - Google Patents

Method of prepn, of positive electrode laminated cell lithium manganate of lithium ion Download PDF

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Publication number
CN1277321C
CN1277321C CNB2004100723416A CN200410072341A CN1277321C CN 1277321 C CN1277321 C CN 1277321C CN B2004100723416 A CNB2004100723416 A CN B2004100723416A CN 200410072341 A CN200410072341 A CN 200410072341A CN 1277321 C CN1277321 C CN 1277321C
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reaction
hours
temperature
accordance
lithium
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CN1601785A (en
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刘锦平
孙新华
赵庆云
宋晓丽
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TIANJIN CHEMICAL RESEARCH & DESIGN INST
China National Offshore Oil Corp CNOOC
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TIANJIN CHEMICAL RESEARCH & DESIGN INST
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention belongs to the technical field of positive electrode material preparation of a lithium ion battery, which is a preparation method of layered lithium manganate of positive electrode material of the lithium ion battery. The present invention is characterized in that a hydrothermal method and a calcining method are organically combined. The technical route comprises: manganese salt and aqueous solution of lithium salt are added to a reaction kettle according to a solid to liquid ratio of 1:10, and the manganese salt is adulterated, and contains Co, Cr and Ni; hydrothermal reaction is carried out at certain temperature, pressure and time, and after the reaction is completed, reaction liquid in the kettle is cooled, filtered, washed and dried; after being dried, the reaction liquid is calcined at high temperature in a roaster furnace, and a layered lithium manganate product is obtained.

Description

The preparation method of positive electrode laminated cell lithium manganate of lithium ion
Technical field
The invention belongs to the technical field of anode material for lithium-ion batteries preparation.
Background technology
Positive electrode is the lithium ion battery important component part.Advantages such as the cobalt acid lithium that the novel anode material LiMn2O4 generally adopts at present has raw material and is easy to get, and is cheap are considered to the most promising positive electrode.LiMn2O4 has two kinds of crystal formations: i.e. spinel-type and stratiform crystal formation.The product of two kinds of crystal formations all exists after charge and discharge cycle repeatedly, the shortcoming that battery capacity descends, but because its initial capacity of layered lithium manganate is 2 times of lithium manganate having spinel structure, therefore many at present is developing focus with the layered lithium manganate.
The following two kinds of methods of the main employing of external layered lithium manganate preparation:
1. hydro thermal method: manganese salt is carried out pre-treatment, generate γ-MnOOH after, place lithium salts, reaction 72hr or longer time under 180 ℃ of temperature and 1.0Mpa pressure, sedimentation and filtration, washing, drying are prepared layered lithium manganate again.The reaction condition HTHP, reaction process is longer cycle time, and made layered lithium manganate battery capacity low slightly be its problem place.
2. calcination method: i.e. manganese salt and sodium salt 700 ℃ of high-temperature calcinations more than 24 hours under inert atmosphere, quenching compressing tablet under liquid nitrogen after calcination process after a while, carries out ion-exchange again in lithium salt solution, generate layered lithium manganate.Equally, twice high-temperature calcination, process cycle is long, energy consumption is very outstanding, and made layered lithium manganate battery cycle characteristics relatively poor be its problem place.
From the above, the visible hydro thermal method or the calcination method of technology as a setting, the technological process cycle is longer, and reaction condition is had relatively high expectations, and energy consumption is bigger, and made separately layered lithium manganate battery performance is lower, is the common problem of its existence.
Summary of the invention
The present invention adopts hydro-thermal-calcination method, promptly two kinds of methods of background technology is organically combined.Major advantage is: hydro-thermal, calcine separately that the time shortens dramatically, the main technique process cycle reduces to 13～18 hours, and energy consumption reduces greatly; And simple to operate, no ion manipulation process; More outstanding is, the layered lithium manganate constant product quality that makes, and make the chemical property of made battery higher, promptly two indexs of initial capacity and cycle characteristics can both the conformance with standard requirement.Effect of the present invention can see Table the battery applications performance test data table of 1. embodiment samples.
The present invention is a kind of preparation method of positive electrode laminated cell lithium manganate of lithium ion, it is characterized in that its process route is: will mix up and contain element Ni and Co, perhaps mix and contain element Ni and Cr and molecular proportion Mn: Ni: Co=0.5: 0.3: 0.2 or Mn: Ni: Cr=0.5: 0.3: 0.2 manganese oxide is to add in reactor at 1: 10 with the lithium hydroxide aqueous solution that is 3～10% weight by solid-to-liquid ratio, 60～80 ℃ of temperature, pressure 0.3～0.8Mpa, carry out hydro-thermal reaction under 6～10 hours time, reaction finishes with the liquid cooling of still internal reaction but, filter, with Cake Wash, dry, in baking furnace, carry out high-temperature calcination after the drying again, 700 ℃～800 ℃ of calcining heats, calcination time 5～10 hours promptly gets the layered lithium manganate product.
The prepared layered lithium manganate capacity of the inventive method (110～140mAh/g) with cobalt acid lithium capacity (＞120mAh/g) suitable, demonstrate cycle characteristics (50 times circulation back capacity still remains on more than 90%) preferably after being assembled into battery.
As selection process route of the present invention and preferred processing condition, in the hydro-thermal reaction that it is characterized in that at first carrying out, the Co that mixes up, Cr, Ni element are respectively its oxide, and lithium hydroxide solution concentration is 5～8% weight, and preferably 5%; Hydrothermal reaction condition is 70～80 ℃ of temperature, pressure 0.5～0.8Mpa, 6～8 hours time, preferably 70 ℃ of temperature, pressure 0.5Mpa, 6 hours time; And in the follow-up high-temperature calcination reaction of carrying out, calcining heat is 700 ℃～750 ℃, calcination time 5～8 hours, and preferably calcining heat is 700 ℃, calcination time is 5 hours.
Execution mode
Embodiment 1
The solution 2L that lithium hydroxide is made into concentration 10% puts into autoclave, simultaneously manganese oxide, nickel oxide, three kinds of materials of cobalt oxide are pressed Mn: Ni: Co=0.5: add at 0.3: 0.2, regulating the interior solid-to-liquid ratio of still is 1: 10, in reaction temperature is 60 ℃, and pressure is to carry out hydro-thermal reaction 8 hours under the condition of 0.8Mpa, after the reaction material is poured out, filter, pull an oar, wash, after the filter cake oven dry, high-temperature calcination is 10 hours in 700 ℃ Muffle furnace, promptly obtains sample A.
Embodiment 2
The solution 2L that lithium hydroxide is made into concentration 5% puts into autoclave, simultaneously manganese oxide, nickel oxide, three kinds of materials of cobalt oxide are pressed Mn: Ni: Co=0.5: add at 0.3: 0.2, regulating the interior solid-to-liquid ratio of still is 1: 10, in reaction temperature is 70 ℃, and pressure is to carry out hydro-thermal reaction 6 hours under the condition of 0.5Mpa, after the reaction material is poured out, filter, pull an oar, wash, after the filter cake oven dry, calcining is 5 hours in 700 ℃ Muffle furnace, promptly obtains sample B.
Embodiment 3
The solution 2L that lithium hydroxide is made into concentration 3% puts into autoclave, simultaneously manganese oxide, nickel oxide, three kinds of materials of chromium oxide are pressed Mn: Ni: Cr=0.5: add at 0.3: 0.2, regulating the interior solid-to-liquid ratio of still is 1: 10, in reaction temperature is 80 ℃, and pressure is to carry out hydro-thermal reaction 10 hours under the condition of 0.3Mpa, after the reaction material is poured out, filter, pull an oar, wash, after the filter cake oven dry, calcining is 5 hours in 800 ℃ Muffle furnace, promptly obtains sample C.
Embodiment 4
This example is the comparative examples of background technology hydro thermal method.
The aqueous solution 2L that lithium hydroxide is made into concentration 5% puts into autoclave, simultaneously manganese oxide, nickel oxide, three kinds of materials of cobalt oxide are pressed Mn: Ni: Co=0.5: add at 0.3: 0.2, regulating the interior solid-to-liquid ratio of still is 1: 10, in reaction temperature is 180 ℃, pressure is reaction 72 hours under the condition of 1.0Mpa, after the reaction material is poured out, filtered, pull an oar, wash, promptly get sample D after the filter cake oven dry.
Embodiment 5
This example is the comparative examples of background technology calcination method.
With manganese oxide, nickel oxide, three kinds of materials of cobalt oxide in Mn: Ni: Co=0.5: (Na: M=1.1: 1) mix, calcining is 24 hours in 700 ℃ Muffle furnace, obtains NaM with NaOH for 0.3: 0.2 ratio xMn 1-xO 2, it is carried out ion-exchange with LiCl again, can obtain sample E.
The battery applications performance test data table of table 1. embodiment sample
Sample Initial charge/discharge capacity (mAh/g) Cycle efficieny is 90% number of times Remarks
A 120/109 50
B 153/133 50
C 116/101 50
D 90/60 50 The hydro thermal method example
E 110/100 30 The calcination method example
(do the application performance test with button cell, the test loop number of times is 50 times)

Claims (7)

1. the preparation method of a positive electrode laminated cell lithium manganate of lithium ion, it is characterized in that its process route is: will mix up and contain element Ni and Co, perhaps mix and contain element Ni and Cr and molecular proportion Mn: Ni: Co=0.5: 0.3: 0.2 or Mn: Ni: Cr=0.5: 0.3: 0.2 manganese oxide is to add in reactor at 1: 10 with the lithium hydroxide aqueous solution that is 3～10% weight by solid-to-liquid ratio, 60～80 ℃ of temperature, pressure 0.3～0.8Mpa, carry out hydro-thermal reaction under 6～10 hours time, reaction finishes with the liquid cooling of still internal reaction but, filter, with Cake Wash, dry, in baking furnace, carry out high-temperature calcination after the drying again, 700 ℃～800 ℃ of calcining heats, calcination time 5～10 hours promptly gets the layered lithium manganate product.
2. in accordance with the method for claim 1, in the hydro-thermal reaction that it is characterized in that at first carrying out, the Co that mixes up, Cr, Ni element are respectively its oxide, and lithium hydroxide solution is 5～8% weight.
3. in accordance with the method for claim 1, it is characterized in that hydrothermal reaction condition is 70～80 ℃ of temperature, pressure 0.5～0.8Mpa, 6～8 hours time.
4. in accordance with the method for claim 1, it is characterized in that calcining heat is 700 ℃～750 ℃ in the follow-up high-temperature calcination reaction of carrying out, calcination time is 5～8 hours.
5. in accordance with the method for claim 2, it is characterized in that lithium hydroxide solution is 5% weight.
6. in accordance with the method for claim 3, it is characterized in that hydrothermal reaction condition is 70 ℃ of temperature, pressure 0.5Mpa, 6 hours time.
7. in accordance with the method for claim 4, it is characterized in that calcining heat is 700 ℃ in the follow-up high-temperature calcination reaction of carrying out, calcination time is 5 hours.
CNB2004100723416A 2004-10-20 2004-10-20 Method of prepn, of positive electrode laminated cell lithium manganate of lithium ion Expired - Fee Related CN1277321C (en)

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1322607C (en) * 2005-04-27 2007-06-20 吉林大学 Method for producing positive pole material-orthorhombic system LiMnO2 of lithium secondary battery
CN1326261C (en) * 2005-05-31 2007-07-11 广州有色金属研究院 Method for preparing layered LiMnO and doping compound
CN100345769C (en) * 2006-03-14 2007-10-31 浙江大学 One step directly preparing process for lithium manganate as lithium ion cell positive pole material
CN101355161B (en) * 2008-09-17 2011-09-28 长沙矿冶研究院 Method for preparing lithium ion battery anode material nickel cobalt lithium manganate
CN103219509B (en) * 2013-04-19 2015-04-01 四川大学 Preparation method of lithium manganese oxide spinel positive material
CN103972487B (en) * 2014-05-16 2016-08-24 厦门钨业股份有限公司 A kind of multicomponent composite oxide material and industrial production process thereof
CN105206824B (en) * 2015-10-23 2018-06-05 福建师范大学 A kind of preparation method of height ratio capacity lithium-rich anode material
CN107394204B (en) * 2017-07-18 2020-10-02 中北大学 Preparation method of layered lithium manganate serving as lithium ion battery anode material
CN107732232A (en) * 2017-10-18 2018-02-23 重庆特瑞新能源材料有限公司 A kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material

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